Titanium oxide composite, titanium oxide composite manufacturing method, and hybrid super capacitor using the same

ABSTRACT

A titanium oxide composite, a titanium oxide composite manufacturing method, and a super capacitor using the same are provided. The titanium oxide composite is prepared to surround graphene on a surface of granule type titanium oxide. One of a granule type Li x Ti y O z  and a granule type H x Ti y O z  is selected and thereby used for the granule type titanium oxide, the granule type Li x Ti y O z  satisfies 1≦x≦4, 1≦y≦5, and 1≦z≦12, and the granule type H x Ti y O z  satisfies 1≦x≦2, 1≦y≦12, and 1≦z≦25.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of Korean Patent Application No. 10-2012-0132500, filed on Nov. 21, 2012, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a titanium oxide composite, a titanium oxide composite manufacturing method, and a super capacitor using the same. More particularly, the present invention relates to a titanium oxide composite in which an electronic conductivity is enhanced by forming graphene to be surrounded on a surface of granule type titanium oxide, a titanium oxide composite manufacturing method, and a hybrid super capacitor using the same.

2. Description of the Related Art

A super capacitor is used for a large capacity energy storage device and technology for electrode materials is under development in order to increase a density of energy to be stored. In view of the battery performance of the super capacitor, a cathode material may play an important role. Lithium-titanium oxide (LTO) has a structurally stable spinel structure as a cathode active material.

Due to a “zero-strain” characteristic that a volume expansion barely occurs in charging and discharging, LTO may have an advantage such as a high cyclic characteristic. Accordingly, LTO has been currently used as a cathode material having a high output and a long lifespan, for example, an electrode material of an ultra high capacity super capacitor.

Korean Laid-Open Publication No. 2011-0013460 discloses a manufacturing method of LTO including mixing lithium carbonate powers or lithium hydroxide powders with titanium oxide by using the titanium oxide as a sintering precursor; using, as the sintering precursor, a titanium and lithium containing compound from a solution containing both titanium and lithium components; and manufacturing a mixture of titanium compound powders and lithium compound by manufacturing a mixture slurry of titanium compound powders and lithium-containing compound and then depositing the lithium compound through spray drying; and using the mixture as the sintering precursor.

The conventional LTO manufactured according to the disclosure of Korean Laid-Open Publication No. 2011-0013460 has a difficult in fast charging and discharging due to a low electronic conductivity. In addition, a theoretical capacity is about 175 mAh/g and thus, is low.

SUMMARY OF THE INVENTION

The present invention provides a titanium oxide composite in which an electronic conductivity is enhanced by forming graphene to be surrounded on a surface of granule type titanium oxide, a titanium oxide composite manufacturing method, and a hybrid super capacitor using the same.

The present invention also provides a titanium oxide composite that may perform fast charging and discharge by forming graphene to be surrounded on a surface of granule type titanium oxide and thereby enhancing an electronic conductivity, a titanium oxide composite manufacturing method, and a hybrid super capacitor using the same.

According to an aspect of the present invention, there is provided a titanium oxide composite, wherein graphene is formed to be surrounded on a surface of granule type titanium oxide. One of a granule type Li_(x)Ti_(y)O_(z) and a granule type H_(x)Ti_(y)O_(z) may be selected and thereby used for the granule type titanium oxide. The granule type Li_(x)Ti_(y)O_(z) may satisfy 1≦x≦4, 1≦y≦5, and 1≦z≦12, the granule type H_(x)Ti_(y)O_(z) may satisfy 1≦x≦2, 1≦y≦12, and 1≦z≦25.

According to another aspect of the present invention, there is provided a method of manufacturing a titanium oxide composite, the method including: coating graphene oxide to be surrounded on a surface of granule type titanium oxide using an electrostatic force; and performing reduction processing of the graphene oxide coated on the surface of the granule type titanium oxide to be graphene.

According to still another aspect of the present invention, there is provided a hybrid super capacitor, including: an anode including a first collector and an anode active material member formed on the first collector; and a cathode including a second collector disposed to face the anode and a cathode active material member formed on the second collector. The anode active material member may include activated carbon, the cathode active material member includes a titanium oxide composite, the titanium oxide composite may include granule type titanium oxide of about 70 wt % to about 99 wt % and graphene of about 1 wt % to about 30 wt %. One of a granule type Li_(x)Ti_(y)O_(z) and a granule type H_(x)Ti_(y)O_(z) may be selected and thereby used for the granule type titanium oxide, the granule type Li_(x)Ti_(y)O_(z) may satisfy 1≦x≦4, 1≦y≦5, and 1≦z≦12, the granule type H_(x)Ti_(y)O_(z) may satisfy 1≦x≦2, 1≦y≦12, and 1≦z≦25.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and/or other aspects of the present invention will become apparent and more readily appreciated from the following description of the exemplary embodiments, taken in conjunction with the accompanying drawings in which:

FIG. 1 is a front view of a titanium oxide composite of the present invention.

FIG. 2 is a front view of granule type titanium oxide of FIG. 1.

FIG. 3 is a front view of graphene of FIG. 1.

FIG. 4 is a process diagram illustrating a process of manufacturing a titanium oxide composite of the present invention.

FIGS. 5 through 8 are flowcharts illustrating embodiments of the process of manufacturing titanium oxide of FIG. 4, respectively.

FIG. 9 is a cross-sectional view of a hybrid super capacitor to which the titanium oxide composite of the present invention is applied.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. Exemplary embodiments are described below to explain the present invention by referring to the figures.

Hereinafter, a titanium oxide composite, a titanium oxide composite manufacturing method, and a hybrid super capacitor using the same according to embodiments of the present invention will be described with reference to the accompanying drawings.

Referring to FIGS. 1 through 3, a titanium oxide composite 10 of the present invention is formed to surround graphene 12 on a surface of granule type titanium oxide 11. The graphene 12 having a specific surface area of 500 m²/g to 2500 m²/g may be used. Such titanium oxide composite 10 may include a granule type titanium oxide of 70 wt % to 99 wt % and graphene of 1 wt % to 30 wt %. To form the graphene 12 so as to be surrounded on the surface of the granule type titanium oxide 11, an electrostatic force occurring between the granule type titanium oxide 11 of which surface positive charge is applied on and graphene oxide 12 a of FIG. 4 having negative charge may be used.

One of a granule type Li_(x)Ti_(y)O_(z) and a granule type H_(x)Ti_(y)O_(z) may be selected and thereby used for the granule type titanium oxide 11. The granule type Li_(x)Ti_(y)O_(z) may satisfy 1≦x≦4, 1≦y≦5, and 1≦z≦12, the granule type H_(x)Ti_(y)O_(z) may satisfy 1≦x≦2, 1≦y≦12, and 1≦z≦25.

The granule type Li_(x)Ti_(y)O_(z) of which an average particle size (D2) of a final phase is 4 μm to 60 μm and of which a specific surface area is 4 m²/g to 100 m²/g may be used. The granule type H_(x)Ti_(y)O_(z) of which an average particle size (D2) of a final phase is 4 μm to 60 μm and of which a specific surface area is 4 m²/g to 100 m²/g may be used. Each of the granule type Li_(x)Ti_(y)O_(z) and the granule type H_(x)Ti_(y)O_(z) may be manufactured using one of disk type, two-fluid nozzle type, and four-fluid nozzle type spray driers.

As compared to the granule type Li_(x)Ti_(y)O_(z), the granule type H_(x)Ti_(y)O_(z) may have a high energy density by about 30%. Since a lithium (Li) precursor is not used, synthesis may be performed in a low temperature, thereby saving manufacturing cost. Accordingly, a hybrid super capacitor having a capacity greater than a hybrid super capacitor using Li_(x)Ti_(y)O_(z) may be embodied.

As described above, the titanium oxide composite 10 of the present invention may enhance an electronic conductivity since the graphene 12 having an excellent conductivity and electron transport capability is coated to be surrounded by the granule type titanium oxide 11 such as the granule type Li_(x)Ti_(y)O_(z) or the granule type H_(x)Ti_(y)O_(z), for example.

Hereinafter, a method of manufacturing a titanium oxide composite constructed as above according to an embodiment of the present invention will be described.

Referring to FIG. 4, the titanium oxide composite manufacturing method of the present invention may coat graphene oxide 12 a to be surrounded on the surface of the granule type titanium oxide 11 using an electrostatic force (S10). When the graphene oxide 12 a is coated to be surrounded on the surface of the granule type titanium oxide 11, reduction processing of the graphene oxide 12 a coated on the surface of the granule type titanium oxide 11 to be the graphene 12 may be performed (S20). Through this, the titanium oxide composite 10 may be manufactured.

To manufacture the titanium oxide composite 10, the method of coating the graphene oxide 12 a to be surrounded on the surface of the granule type titanium oxide 11 may prepare the granule type titanium oxide 11 (S11).

When the granule type titanium oxide 11 is prepared, positive charge may be applied by coating NH₂ on the surface of the granule type titanium oxide 11 (S12). NH₂ for applying the positive charge on the surface of the granule type titanium oxide 11 may be coated on the surface of the granule type titanium oxide 11 using APTMS (3-aminopropyl-trimethoxysilane).

When the positive charge is applied on the surface of the granule type titanium oxide 11, the graphene oxide 12 a having negative charge may be coated to be surrounded on the surface of the granule type titanium oxide 11 having the positive charge using an electrostatic force (S13). The graphene oxide 12 a coated on the surface of the granule type titanium oxide 11 may be manufactured through a chemical oxidation and reduction processing using a HUMMER method. The graphene oxide 12 a coated on the surface of the granule type titanium oxide 11 may be reduced to be the graphene 12 using hydrazine (N₂H₄).

One of a granule type Li_(x)Ti_(y)O_(z) and a granule type H_(x)Ti_(y)O_(z) may be selected and thereby used for the granule type titanium oxide 11 used to surround the graphene oxide 12 a. The granule type Li_(x)Ti_(y)O_(z) may be formed using one of a solid phase method, a sol-gel method, and a hydrothermal synthetic method. The granule type H_(x)Ti_(y)O_(z) may be formed using the solid phase method after ion exchange.

Hereinafter, a method of forming the granule type Li_(x)Ti_(y)O_(z) or the granule type H_(x)Ti_(y)O_(z) in operation S11 of preparing the granule type titanium oxide 11 will be further described.

Referring to FIG. 5, a method of forming the granule type Li_(x)Ti_(y)O_(z) using the solid phase method may prepare a plurality of lithium (Li) precursors and a plurality of titanium (Ti) precursors (S111). One of LiOH and Li₂CO₃ may be selected and thereby used for each of the plurality of lithium (Li) precursors. One of TiO₂, TiO(OH)₂, and Ti(OCH₂CH₂O) may be selected and thereby used for each of the plurality of titanium (Ti) precursors.

When the plurality of lithium (Li) precursors and the plurality of titanium (Ti) precursors is prepared, a plurality of primary phases 11 a having an average particle size D1 (see FIG. 2) of 100 nm to 800 nm may be formed by applying an ultrasound or mechanical mixing method to the plurality of lithium (Li) precursors and the plurality of titanium (Ti) precursors (S112). Here, the mechanical mixing method may refer to a ball-mill method, for example.

When the plurality of primary phases 11 a is formed, the plurality of primary phases 11 a may be dried using one of a spray drier (not shown) and a mechano-chemical reaction method (S113). A spray drier having two-fluid or four-fluid nozzle may be used to dry the plurality of primary phases 11 a.

When the plurality of primary phases 11 a is dried, a final phase granule type Li_(x)Ti_(y)O_(z) having an average particle size D2 (see FIG. 2) of 4 μm to 60 μm may be formed by performing a heat treatment on the plurality of primary phases 11 a under the atmosphere of 700° C. to 900° C. for 2 to 12 hours (S114). Here, the final phase granule type Li_(x)Ti_(y)O_(z) may be formed to satisfy 1≦x≦4, 1≦y≦5, and 1≦z≦12. An embodiment of the final phase granule type Li_(x)Ti_(y)O_(z), that is, a chemical reaction formula of Li₄Ti₅O₁₂ may be “5TiO₂+2Li₂CO₃→Li₄Ti₅O₁₂+2CO_(2↑)”.

Referring to FIG. 6, a method of forming the granule type Li_(x)Ti_(y)O_(z) using the sol-gel method may prepare a plurality of LiNO₃ (lithium nitrate) precursors and a plurality of Ti[OCH(CH₃)₂]₄ (tetrabutyl orthotinate) precursors (S121). When the plurality of LiNO₃ precursors and the plurality of Ti[OCH(CH₃)₂]₄ precursors is prepared, the plurality of LiNO₃ precursor and the plurality of Ti[OCH(CH₃)₂]₄ precursors may be dissolved using ethanol or distilled water and then be in a gel state by increasing viscosity using a spin drier (S122). When the gel is manufactured, a dried material may be manufactured by drying the gel at 80° C. to 100° C. for 12 to 72 hours using a forced-circulation oven (S123). When the dried material is manufactured, the final phase granule type Li_(x)Ti_(y)O_(z) having an average particle size D2 (see FIG. 2) of 4 μm to 60 μm may be formed by performing a heat treatment on the dried material under the atmosphere of 80° C. to 100° C. (S124). The heat treatment on the dried material may be performed using a spray dry method or a mechano-chemical reaction method.

Referring to FIG. 7, a method of forming the granule type Li_(x)Ti_(y)O_(z) using the hydrothermal synthetic method may prepare LiOH·H₂O (lithium hydroxide mono-hydrate) and Ti(OC₄H₉)₄ (tetrabutyl titanate) (S131). When LiOH·H₂O and Ti(OC₄H₉)₄ are prepared, a solution of Ti(OC₄H₉)₄ may be prepared by mixing Ti(OC₄H₉)₄ and ethanol (S132). When the solution of Ti(OC₄H₉)₄ is prepared, a mixture of Ti(OC₄H₉)₄ and LiOH·H₂O may be prepared by mixing LiOH·H₂O into the solution of Ti(OC₄H₉)₄ (S133). The mixture of Ti(OC₄H₉)₄ and LiOH·H₂O may be prepared by dropping LiOH·H₂O into the solution of Ti(OC₄H₉)₄. When the mixture of Ti(OC₄H₉)₄ and LiOH·H₂O is prepared, the final phase granule type Li_(x)Ti_(y)O_(z) having an average particle size D2 (see FIG. 2) of 4 μm to 60 μm may be formed by performing a hydrothermal synthesis on the mixture of Ti(OC₄H₉)₄ and LiOH·H₂O at 130C to 200° C. using autoclave (S134).

Referring to FIG. 8, a method of forming the granule type H_(x)Ti_(y)O_(z) using the solid phase method after ion exchange may prepare a plurality of sodium (Na) precursors and a plurality of titanium (Ti) precursors (S141). Here, one of Na₂CO₃, NaOH, and Na₂O may be selected and thereby used for each of the plurality of sodium (Na) precursors, and each of TiO₂, TiO(OH)₂, and Ti(OCH₂CH₂O) may be selected and thereby used for each of the plurality of titanium (Ti) precursors.

When the plurality of sodium (Na) precursors and the plurality of titanium (Ti) precursors is prepared, a plurality of primary phases 11 a having an average particle size D1 (see FIG. 2) of 10 nm to 500 nm may be formed by applying an ultrasound or mechanical mixing method to the plurality of sodium (Na) precursors and the plurality of titanium (Ti) precursors (S142). When the plurality of primary phases 11 a is formed, the plurality of primary phases 11 a may be dried in an oven at 60° C. to 100° C. for 10 to 20 hours (S143).

When the plurality of primary phases 11 a is dried, a granule type Na_(x)Ti_(y)O_(z) may be formed by performing a heat treatment on the dried primary phases 11 a under the atmosphere of 700° C. to 800° C. for 24 to 48 hours (S144). The granule type Na_(x)Ti_(y)O_(z) may be formed to satisfy 1≦x≦2, 1≦y≦3, and 1≦z≦7. An embodiment of the granule type Na_(x)Ti_(y)O_(z), that is, a chemical reaction formula of Na₂Ti₃O₇ may be “3TiO₂+Na₂CO₃→Na₂Ti₃O₇ +CO₂T”. When the granule type Na_(x)Ti_(y)O_(z) is formed, the granule type H_(x)Ti_(y)O_(z) may be formed by processing the granule type Na_(x)Ti_(y)O_(z) in a chloride solution of 60° C. to 70° C. for 3 to 5 days and thereby performing ion exchange (S145). Here, the granule type H_(x)Ti_(y)O_(z) may be formed by exchanging sodium (Na) ions include in the granule type Na_(x)Ti_(y)O_(z) to be hydrogen (H) ions using hydrogen chloride (HCl) having a concentration of 0.1 mol to 1 mol (M) in the chloride (HCl) solution.

When the granule type H_(x)Ti_(y)O_(z) is formed, the granule type H_(x)Ti_(y)O_(z) may be neutralized to have a pH of 7 to 8 using water or ethanol (S146). When the granule type H_(x)Ti_(y)O_(z) is neutralized to have a pH of 7 to 8, the granule type H_(x)Ti_(y)O_(z) may be dried using a spray drier (S147). When the granule type H_(x)Ti_(y)O_(z) is dried, the final phase granule type H_(x)Ti_(y)O_(z) having an average particle size D2 (see FIG. 2) of 4 μm to 60 μm may be formed by performing a heat treatment on the dried granule type H_(x)Ti_(y)O_(z) under the atmosphere of 250° C. to 350° C. for 5 to 10 hours (S148). The final phase granule type H_(x)Ti_(y)O_(z) may be formed to satisfy 1≦x≦2, 1≦y≦12, and 1≦z≦25. An embodiment of the final phase granule type H_(x)Ti_(y)O_(z) may be H₂Ti₁₂O₂₅.

Hereinafter, a hybrid super capacitor using the titanium oxide composite 10 manufactured according to the titanium oxide composite manufacturing method of the present invention will be described.

Referring to FIG. 9, a hybrid super capacitor 100 of the present invention may include an anode 110, a cathode 120, an electrolyte 130, a separating film 140, a receiving case 150, and lead members 160 and 170.

The anode 110 may include a first collector 111 and an anode active material member 112. The anode active material member 112 may include activated carbon, and may be formed on a whole surface of one side of the first collector 111. The cathode 120 may include a second collector 121 disposed to face the anode 110 and a cathode active material member 122. The cathode active material member 122 may be formed on a whole surface of another side of the second collector 121, and may use the titanium oxide composite of the present invention. The titanium oxide composite may include a granule type titanium oxide of 70 wt % to 99 wt % and graphene of 1 wt % to 30 wt %. One of a granule type Li_(x)Ti_(y)O_(z) and a granule type H_(x)Ti_(y)O_(z) may be selected and thereby used for the granule type titanium oxide 11. The granule type Li_(x)Ti_(y)O_(z) may satisfy 1≦x≦4, 1≦y≦5, and 1≦z≦12, and the granule type H_(x)Ti_(y)O_(z) may satisfy 1≦x≦2, 1≦y≦12, and 1≦z≦25.

The electrolyte 130 may be formed between the anode 110 and the cathode 120, and lithium salt may be used. Such lithium salt may use one of LiClO₄, LiN(CF₄SO2)₂, LiBF₄, LiCF₃SO₃, LiPF₆, LiSbF₆, and LiAsF₆. The separating film 140 may be formed between the anode 110 and the cathode 120 to thereby prevent the anode 110 and the cathode 120 from being electrically connected in contact with each other and thereby being shorted. A porous separating film may be used. One of polypropylene base, polyethylene base, and polyolefin base may be used for the porous separating film. The receiving case 150 may be mounted to be inserted with each of the anode 110, the cathode 120, the electrolyte 130, and the separating film 140. The lead members 160 and 170 may be connected to the first collector 111 of the anode 110 and the second collector 121 of the cathode 120, respectively. As described above, the hybrid super capacitor 100 of the present invention may enhance an electronic conductivity by using the titanium oxide composite 10 as the cathode active member 122, thereby enabling fast charging and discharging.

As described above, a titanium oxide composite, a titanium oxide composite manufacturing method, and a hybrid super capacitor according to the present invention may enhance an electronic conductivity by forming graphene to be surrounded on a surface of granule type titanium oxide, thereby enabling fast charging and discharging.

Although a few exemplary embodiments of the present invention have been shown and described, the present invention is not limited to the described exemplary embodiments. Instead, it would be appreciated by those skilled in the art that changes may be made to these exemplary embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents. 

What is claimed is:
 1. A titanium oxide composite, wherein graphene is formed to be surrounded on a surface of granule type titanium oxide.
 2. The titanium oxide composite of claim 1, wherein one of a granule type Li_(x)Ti_(y)O_(z) and a granule type H_(x)Ti_(y)O_(z) is selected and thereby used for the granule type titanium oxide, and wherein the granule type Li_(x)Ti_(y)O_(z) satisfies 1≦x≦4, 1≦y≦5, and 1≦z≦12, and the granule type H_(x)Ti_(y)O_(z) satisfies satisfy 1≦x≦2, 1≦y≦12, and 1≦z≦25.
 3. The titanium oxide composite of claim 1, wherein one of a granule type Li_(x)Ti_(y)O_(z) and a granule type H_(x)Ti_(y)O_(z) is selected and thereby used for the granule type titanium oxide, wherein the granule type Li_(x)Ti_(y)O_(z) of which an average particle size of a final phase is about 4 μm to about 60 μm and of which a specific surface area is about 4 m²/g to about 100 m²/g is used, and the granule type H_(x)Ti_(y)O_(z) of which an average particle size of a final phase is about 4 μm to about 60 μm and of which a specific surface area is about 4 m²/g to about 100 m²/g is used, and wherein each of the granule type Li_(x)Ti_(y)O_(z) and the granule type H_(x)Ti_(y)O_(z) is manufactured using one of disk type, two-fluid nozzle type, and four-fluid nozzle type spray driers.
 4. The titanium oxide composite of claim 1, wherein the graphene having a specific surface area of about 500 m²/g to about 2500 m²/g is used.
 5. The titanium oxide composite of claim 1, wherein the titanium oxide composite comprises the granule type titanium oxide of about 70 wt % to about 99 wt % and the graphene of about 1 wt % to about 30 wt %.
 6. A method of manufacturing a titanium oxide composite, the method comprising: coating graphene oxide to be surrounded on a surface of granule type titanium oxide using an electrostatic force; and performing reduction processing of the graphene oxide coated on the surface of the granule type titanium oxide to be graphene.
 7. The method of claim 6, wherein the coating of the graphene oxide comprises: preparing the granule type titanium oxide; applying positive charge by coating NH₂ on the surface of the granule type titanium oxide; and coating, using the electrostatic force, the graphene oxide having negative charge to be surrounded on the surface of the granule type titanium oxide having the positive charge, and wherein, in the preparing of the granule type titanium oxide, one of a granule type Li_(x)Ti_(y)O_(z) and a granule type H_(x)Ti_(y)O_(z) is selected and thereby used for the granule type titanium oxide, the granule type Li_(x)Ti_(y)O_(z) is formed using one of a solid phase method, a sol-gel method, and a hydrothermal synthetic method, and the granule type H_(x)Ti_(y)O_(z) is formed using the solid phase method after ion exchange.
 8. The method of claim 7, wherein the forming of the granule type Li_(x)Ti_(y)O_(z) using the solid phase method in the preparing of the granule type titanium oxide comprises: preparing a plurality of lithium (Li) precursors and a plurality of titanium (Ti) precursors; forming a plurality of primary phases having an average particle size of about 100 nm to about 800 nm by applying an ultrasound or mechanical mixing method to the plurality of lithium (Li) precursors and the plurality of titanium (Ti) precursors; drying the plurality of primary phases using one of a spray drier and a mechano-chemical reaction method; and forming a final phase granule type Li_(x)Ti_(y)O_(z) having an average particle size of about 4 μm to about 60 μm by performing a heat treatment on the plurality of primary phases under the atmosphere of about 700° C. to about 900° C. for about 2 to about 12 hours, wherein in the preparing of the plurality of lithium (Li) precursors and the plurality of titanium (Ti) precursors, one of LiOH and Li₂CO₃ is selected and thereby used for each of the plurality of lithium (Li) precursors and one of TiO₂, TiO(OH)₂, and Ti(OCH₂CH₂O) is selected and thereby used for each of the plurality of titanium (Ti) precursors, and wherein in the forming of the final phase granule type Li_(x)Ti_(y)O_(z), the granule type Li_(x)Ti_(y)O_(z) satisfies 1≦x≦4, 1≦y≦5, and 1≦z≦12.
 9. The method of claim 7, wherein the forming of the granule type Li_(x)Ti_(y)O_(z) using the sol-gel method in the preparing of the granule type titanium oxide comprises: preparing a plurality of LiNO₃ precursors and a plurality of Ti[OCH(CH₃)₂]₄ precursors; dissolving the plurality of LiNO₃ precursors and the plurality of Ti[OCH(CH₃)₂]₄ precursors to be in a gel state using ethanol or distilled water; manufacturing a dried material by drying the gel at about 80° C. to about 100° C. for about 12 to about 72 hours; and forming the granule type Li_(x)Ti_(y)O_(z) by performing a heat treatment on the dried material under the atmosphere of about 80° C. to about 100° C.
 10. The method of claim 7, wherein the forming of the granule type Li_(x)Ti_(y)O_(z) using the hydrothermal synthetic method in the preparing of the granule type titanium oxide comprises: preparing LiOH·H₂O and Ti(OC₄H₉)₄; preparing a solution of Ti(OC₄H₉)₄ by mixing Ti(OC₄H₉)₄ and ethanol; preparing a mixture of Ti(OC₄H₉)₄ and LiOH·H₂O by mixing LiOH·H₂O into the solution of Ti(OC₄H₉)₄; and forming the granule type Li_(x)Ti_(y)O_(z) by performing a hydrothermal synthesis on the mixture of Ti(OC₄H₉)₄ and LiOH·H₂O at about 130° C. to about 200° C.
 11. The method of claim 7, wherein the forming of the granule type H_(x)Ti_(y)O_(z) using the solid phase method in the preparing of the granule type titanium oxide comprises: preparing a plurality of sodium (Na) precursors and a plurality of titanium (Ti) precursors; forming a plurality of primary phases having an average particle size of about 10 nm to about 500 nm by applying an ultrasound or mechanical mixing method to the plurality of sodium (Na) precursors and the plurality of titanium (Ti) precursors; drying the plurality of primary phases in an oven at about 60° C. to 100° C. for about 10 to about 20 hours; forming a granule type Na_(x)Ti_(y)O_(z) by performing a heat treatment on the dried primary phases under the atmosphere of about 700° C. to about 800° C. for about 24 to about 48 hours; forming the granule type H_(x)Ti_(y)O_(z) by processing the granule type Na_(x)Ti_(y)O_(z) in a chloride solution of about 60° C. to about 70° C. for three to five days and thereby performing ion exchange; neutralizing the granule type H_(x)Ti_(y)O_(z) to have a pH of 7 to 8 using water or ethanol; drying the granule type H_(x)Ti_(y)O_(z) using a spray drier; and forming a final phase granule type H_(x)Ti_(y)O_(z) having an average particle size of about 4 μm to about 60 μm by performing a heat treatment on the dried granule type H_(x)Ti_(y)O_(z) under the atmosphere of about 250° C. to about 350° C. for about 5 to about 10 hours, wherein in the preparing of the plurality of sodium (Na) precursors and the plurality of titanium (Ti) precursors, one of Na₂CO₃, NaOH, and Na₂O is selected and thereby used for each of the plurality of sodium (Na) precursors, and one of TiO₂, TiO(OH)₂, and Ti(OCH₂CH₂O) is selected and thereby used for each of the plurality of titanium (Ti) precursors, and wherein in the forming of the granule type Na_(x)Ti_(y)O_(z), Na_(x)Ti_(y)O_(z) satisfies 1≦x≦2, 1≦y≦3, and 1≦z≦7, in the forming of the granule type H_(x)Ti_(y)O_(z), the granule type H_(x)Ti_(y)O_(z) satisfies 1≦x≦2, 1≦y≦12, and 1≦z≦25, and a concentration of hydrogen chloride (HCl) in the chloride solution is about 0.1 to about 1 mol.
 12. The method of claim 7, wherein in the applying of the positive charge by coating NH₂ on the surface of the granule type titanium oxide, NH₂ is coated on the surface of the granule type titanium oxide using APTMS (3-aminopropyl-trimethoxysilane).
 13. The method of claim 6, wherein the performing of the reduction processing comprises reducing the graphene oxide to be graphene using hydrazine (N₂H₄).
 14. A hybrid super capacitor, comprising: an anode comprising a first collector and an anode active material member formed on the first collector; and a cathode comprising a second collector disposed to face the anode and a cathode active material member formed on the second collector, wherein the anode active material member comprises activated carbon, the cathode active material member comprises a titanium oxide composite, the titanium oxide composite comprises granule type titanium oxide of about 70 wt % to about 99 wt % and graphene of about 1 wt % to about 30 wt %, and wherein one of a granule type Li_(x)Ti_(y)O_(z) and a granule type H_(x)Ti_(y)O_(z) is selected and thereby used for the granule type titanium oxide, the granule type Li_(x)Ti_(y)O_(z) satisfies 1≦x≦4, 1≦y≦5, and 1≦z≦12, and the granule type H_(x)Ti_(y)O_(z) satisfies 1≦x≦2, 1≦y≦12, and 1≦z≦25. 